Curable coating compositions

ABSTRACT

A curable coating composition that exhibits improved cure and adhesion to various substrates, especially synthetic textiles used in the manufacture of air bags, comprises a composition curable by a hydrosilylation reaction, an acryloxy functional alkoxysilane or a methacryloxy functional alkoxysilane, an alkenyl functional silanol terminated organopolysiloxane, and an epoxy functional alkoxysilane. The curable coating composition is especially useful for application to synthetic textiles such as automotive air bags.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 11/791,098 filed 17 May 2007, now issued as U.S.Pat. No. 8,058,190, which is a U.S. national stage filing under 35U.S.C. §371 of PCT Application No. PCT/US2005/040200 filed on 7 Nov.2005, which claims the benefit of U.S. Provisional Patent ApplicationNo. 60/649,051 filed 1 Feb. 2005 under 35 U.S.C. §119 (e). PCTApplication No. PCT/US2005/040200 and U.S. Provisional PatentApplication No. 60/649,051 are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

This invention is directed to curable coating compositions that adherewell to a variety of substrates, especially automotive air bags. It isparticularly suitable for application to synthetic textiles, such asfiber base cloths consisting of fabrics made from polyamide fibers suchas Nylon 6, Nylon 46, and Nylon 66; aramid fibers such as copolymers ofp-phenylene terephthalamide and aromatic ethers; polyester fibers suchas polyalkylene terephthalate; aromatic polyester fibers; vinylonfibers; rayon fibers; polyolefin fibers such as super high molecularweight polyethylene; polyoxymethylene fibers; sulfone fibers such asp-phenylene sulfones and polysulfones; polyetherimide fibers; and carbonfibers. Fabrics made of polyamide fibers and the fabrics made ofpolyester fibers are preferred.

Self-adhering coating compositions are generally known that cure by ahydrosilylation reaction. They contain additives that aid adhesion to avariety of substrates, thereby obviating the need for application of aprimer composition prior to coating. It is an important criterion in theindustrial manufacture of certain coated substrates, for example,synthetic textiles, that the coating process and the subsequent adhesivebonding between the substrate and the cured coating be achieved asrapidly as possible, to meet ever increasing demands on manufacturingoutput. There is therefore a continuing need to provide curable coatingcompositions that may be coated easily onto a suitable substrate, thatare able to cure rapidly, and that achieve adhesion to the substratequicker than heretofore possible, and without adversely affecting thephysical properties of the cured material.

According to this invention, it has been found that curable coatingcompositions can be provided and easily coated onto suitable substratesand cured, with the concomitant rapid onset of adhesion, by usingcertain compounds as adhesion promoting additives.

BRIEF SUMMARY OF THE INVENTION

The invention is therefore directed to a curable coating compositioncomprising a composition curable by a hydrosilylation reaction; anacryloxy functional alkoxysilane or a methacryloxy functionalalkoxysilane; an alkenyl functional silanol terminatedorganopolysiloxane; and an epoxy functional alkoxysilane.

Curable coating compositions according to the invention possess numerousadvantages. Such coating compositions for example are able to cure andat the same time rapidly develop an adhesive bond to a variety ofsubstrates, in particular to certain synthetic textiles, for examplepolyesters and polyamides such as Nylon 66. Thereafter, the curedcoating composition exhibits good resistance to heat aging and humidityaging, and the adhesive bond to the substrate is virtually unchangedafter humidity aging of 95 percent relative humidity (RH) at 70° C.These and other features of the invention will become apparent from aconsideration of the detailed description.

BRIEF DESCRIPTION OF THE DRAWING

None

DETAILED DESCRIPTION OF THE INVENTION

Component (A) of the curable coating composition according to theinvention is a composition curable by a hydrosilylation reaction.Operative compositions are those well known in the art. The compositioncurable by a hydrosilylation reaction (A) includes three components(i)-(iii). Component (i) of the composition curable by a hydrosilylationreaction (A) is an organopolysiloxane having at least two silicon bondedalkenyl groups per molecule. Component (ii) of the composition curableby a hydrosilylation reaction (A) is an organohydrogensiloxane having atleast three silicon bonded hydrogen atoms per molecule. Component (iii)of the composition curable by a hydrosilylation reaction (A) is a noblemetal catalyst.

Component (A)(i) can be any organopolysiloxane having at least twosilicon bonded alkenyl groups per molecule, and generally consists ofpolymers varying from viscous materials to freely flowing liquids. It ispreferred that at least some, preferably most, of the organopolysiloxanehaving silicon bonded alkenyl groups have a viscosity of not greaterthan 100 Pa·s at 25° C., more preferably 1-60 Pa·s at 25° C. Theseorganopolysiloxanes may be homopolymers, copolymers, or mixtures ofhomopolymers and copolymers. The organopolysiloxanes contain units ofthe formula R_(a)R′_(b)SiO_([4−a+b)]/2), wherein R is a monovalenthydrocarbon group, R′ is a monovalent unsaturated hydrocarbon group, ais 0, 1, 2 or 3, and b is 0 or 1; provided that a+b is not greater than3.

Component (A)(ii) are organohydrogensiloxanes having at least threesilicon bonded hydrogen atoms, that function as the curing agent for thehydrosilylation reaction. These organohydrogensiloxanes may also varyfrom viscous materials to freely flowing liquids. Preferred materialshave a viscosity of not greater than 500 mPa·s at 25° C., morepreferably 5-55 mPa·s at 25° C. The organohydrogensiloxanes may behomopolymers, copolymers, or mixtures of homopolymers and copolymers.The organohydrogensiloxanes contain units of the formulaR_(a)H_(b)SiO_([4−(a+b)]/2), wherein R, a, and b are as defined above.

Component (A)(iii) of the composition curable by a hydrosilylationreaction is a noble metal catalyst for the reaction of the alkenylsubstituted organopolysiloxane (A)(i) with the organohydrogensiloxane(A)(ii). The noble metal catalyst may be a rhodium or platinumcontaining material. Platinum catalysts are preferred, and may take anyof the known forms, ranging from platinum deposited onto carriers suchas powdered charcoal, to platonic chloride, salts of platinum,chloroplatinic acids, and encapsulated forms thereof. A preferred formof platinum catalyst is chloroplatinic acid, either in the form of thecommonly obtainable hexahydrate, or in the anhydrous form. Platinumcomplexes may also be used such as those prepared from chloroplatinicacid hexahydrate, and divinyltetramethyldisiloxane.

The curable coating composition according to the invention includes ahydrosilylation reaction inhibitor (B). Inhibitors for hydrosilylationreactions, especially those catalyzed by platinum based catalysts, areknown and include, for example, acetylenic alcohols, dialkyl maleates,primary alcohols, or mixtures thereof. The hydrosilylation reactioninhibitor may be exemplified by acetylenic alcohols such as3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol,1-ethynyl-1-cyclohexanol, and phenylbutynol; ene-yne compounds such as3-methyl-3-penten-1-yne, and 3,5-dimethyl-3-hexen-1-yne;tetramethyltetrahexenylcyclotetrasiloxane; and benzotriazole. Thehydrosilylation reaction inhibitor is preferably present in the curablecoating composition in a proportion sufficient to ensure that thecoating composition cures. If no hydrosilylation reaction inhibitor ispresent, then the adhesion of the coating composition to a substrate maybe negatively influenced, and if the concentration of the inhibitor istoo high, the composition may fail to cure quickly enough.

The silicone resin component (C) may be any silicone compound having aresinous structure, but it preferably is an MQ resin consistingessentially of monovalent siloxane units M, and tetravalent siloxaneunits Q, and preferably a resin consisting essentially of M unitsR′R₂SiO_(1/2) and R₃SiO_(1/2), and Q units SiO_(4/2), in which R and R′are as defined above; provided at least one R′ group is present permolecule. It's preferred that R is an alkyl group or an aryl grouphaving 1-18 carbon atoms, more preferably an alkyl group having 1-8carbon atoms, such as methyl, ethyl, isopropyl, hexyl, and octyl.Preferably, R′ is an alkenyl group having terminal unsaturation, meaningthat the unsaturation is between the two carbon atoms that are furthestremoved from the silicon atom. The alkenyl group can have 2-8 carbonatoms, preferably the vinyl group, provided there is no more than 10percent by weight of vinyl groups per molecule, preferably 1-5 percentby weight of vinyl groups per molecule. In some cases, it may bedesirable to treat the silicone resin (C) with treating agents such ashexamethyldisilazane and methyltrimethoxysilane. The silicone resin (C)may be in solid or liquid form, although it is preferred that the ratioof the units M to the units Q be such that the resin is a solid atambient temperature and pressure, i.e., an M/Q ratio of 0.6/1 to 1.8/1,preferably 1.2/1 to 1.6/1. The silicone resin can be in the form of a 60percent solution of the resin in a solvent such as xylene or toluene.

The adhesion promoting additive (D) of the coating composition of theinvention includes four components (i)-(v). Adhesion promoting additive(D)(i) is an acryloxy functional alkoxysilane or a methacryloxyfunctional alkoxysilane. Some representative examples of suitablealkoxysilanes are for example 3-acryloxypropyldimethylmethoxysilane,3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane,3-methacryloxymethyldimethylethoxysilane,3-methacryloxymethyltriethoxysilane,3-methacryloxymethyltrimethoxysilane,3-methacryloxypropyldimethylethoxysilane,3-methacryloxypropyldimethylmethoxysilane,3-methacryloxypropylmethyldiethoxysilane,3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropyltriethoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropyltrisisopropoxysilane, and3-methacryloxypropyltrismethoxyethoxysilane. Component (D)(i) ispreferably used at concentrations of from 0.1-2 percent by weight of thetotal weight of the coating composition, preferably 0.3-1 percent byweight. Higher amounts may be desirable in instances where the coatingcomposition is to be applied to certain textile substrates such aspolyesters.

Component (ii) of adhesion promoting additive (D) is an organotitaniumcompound. This compound serves to catalyze the reaction of thecomponents of the adhesion promoting additive (D). Component (ii) may beany organotitanium compound having organic groups attached to titaniumthrough a titanium-oxygen-carbon linkage, especially ortho-esters thatare alcoholates or acylates in which the organic group is derived from acarboxylic acid. The organotitanium compound may also contain bothalcoholate and acylate groups attached to the same titanium atom. Somerepresentative organotitanium compounds include compounds of the formulaTi(OR″)₄, wherein R″ is an alkyl group, an alkoxyalkyl group, or an acylgroup, such as tetraisopropoxytitanate, tetramethoxyethoxytitanate, anddiisopropyldiacetoxytitanate. Useful organotitanium compounds includechelated or partially chelated titanium compounds. These compounds canbe prepared by reacting an alcoholate as referred to above, with adiketone or a derivative thereof. Especially useful are the partiallychelated titanium compounds having two alcoholate groups attached totitanium.

The presence of a catalytic amount of the organotitanium compound in theadhesion promoting additive (D) promotes the rapid onset of adhesion ofthe curable coating composition to the substrate, and in addition, itpromotes the rapid onset of adhesion that does not deteriorate overtime. The organotitanium compounds should be a compound that does notproduce toxic vapors as by-products or that generates unpleasant odorsthat can accompany certain organotitanium compounds.

The alkenyl functional silanol terminated organopolysiloxane component(iii) of the adhesion promoting additive (D) contains unitscorresponding to the formula R² _(c)R′SiO_((3-c)/2) and R²_(d)SiO_((4-d)/2), wherein R² is an alkyl group having 1-8 carbon atoms,or an aryl group having 6-8 carbon atoms; R′ is a monovalent unsaturatedalkenyl or alkynl group; c is 1 or 2, and d is 1, 2 or 3. Preferably,component (iii) corresponds to the formula H—(OSiR²₂)_(m)(OSiR²R′)_(n)—OH wherein R² and R′ are as defined above; R′ has2-8 carbon atoms; m is 1-6, preferably 2-5, and n is 1-6, preferably1-3. The preferred component (iii) should have from 10-15 percent byweight of silicon bonded alkenyl groups, preferable vinyl groups, permolecule. Most useful are those polymers having a relatively low alkenylcontent such that they do not significantly compete with thehydrosilylation reaction of component (A) of the coating composition.Component (iii) may be included in the adhesion promoting additive (D)in proportions of from 30 to 75 parts by weight per 100 parts ofcomponent (D)(i).

The metal chelate compounds (iv) of the adhesion promoting additive (D)function to enhance the adhesion promoting characteristics of theadhesion promoting additive (D). Any metal chelate that is compatiblewith the coating composition, and that does not interfere with thehydrosilylation reaction of the constituents of component (A), issuitable. Some examples of metal chelates include acetyl acetonates suchas triacetyl acetonates of aluminium, tetraacetyl acetonates ofzirconium, and triacetylacetonates of iron. Aluminium chelates arepreferred wherein the aluminium is chelated with 1,3-diketones such asacetylacetonate, or hydroxycarboxylic acids such as tartaric acid. Themost preferred aluminium chelate is aluminium acetylacetonate. Aluminiumchelates enhance and increase the rate of adhesion of the coatingcomposition and the substrate. The metal chelate may be present in thecoating composition in proportions of 1-50 parts by weight per 100 partsby weight of component (D)(i), preferably 1-3 parts by weight per 100parts of component (D)(i), or 0.004 to 0.3 percent by weight of thecoating composition. Higher levels of metal chelates may impair theflame resistance of the curable coating composition.

Component (v) of the adhesion promoting additive (D) is an epoxyfunctional alkoxysilane. Some representative examples of suitable epoxyfunctional alkoxysilanes are for example2-(3,4-epoxycyclohexyl)ethyltriethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,5,6-epoxyhexyltriethoxysilane, 3-glycidoxypropyldimethylethoxysilane,3-glycidoxypropylmethyldiethoxysilane,3-glycidoxypropylmethyldimethoxysilane,3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyltrimethoxysilane.

The adhesion promoting additive (D) may be present in the curablecoating composition in an amount that is 0.1-3.2 percent by weight ofthe total weight of the curable coating composition.

Component (E) of the curable coating composition is an inorganic fillerthat may be selected from those fillers known in the silicone rubber artfor reinforcement, viscosity adjustment, improving heat resistance, andimproving flame retardancy. The inorganic filler (E) may be exemplifiedby reinforcing fillers such as fumed titanium oxide; microparticulatesilicas including fumed silica, precipitated silica, and calcinedsilica; nonreinforcing fillers such as quartz powder, diatomaceousearth, iron oxide, aluminum oxide, calcium carbonate, and magnesiumcarbonate; and by any of these fillers that have been treated with anorganosilicon compound such as an organosilane, an organosiliazane, oran organopolysiloxane.

Among these fillers, ultramicroparticulate silicas with a particlediameter of 50 millimicron and more, and a specific surface area of 50or less m²/g, are especially useful. Surface treated silica is even morepreferred. A surface treated silica is a silica whose surface has beenpreliminarily treated with an organosilane, an organosilazane such ashexamethyldisilazane, or a diorganocyclopolysiloxane. If desired, thesurface of the filler can also be treated with a vinyl functionalorganosilane, a vinyl functional organosilazane, or with component (iii)of the adhesion promoting additive (D). The quantity of addition ofComponent (E) will vary with the type of inorganic filler, but generallywill be within the range of 5-10 percent by weight of the curablecoating composition. Other adjuvants may also be added to the curablecoating composition such as metal carbonates; pigments; catalystinhibitors; heat stabilizers; and bath life extenders.

Component (F) of the curable coating composition is a cyclic alkenylgroup bearing polysiloxane. Some examples of Component (F) include1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane,1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane,pentavinylpentamethylcyclopentasiloxane, and1,3,5,7-tetra-allyl-1,3,5,7-tetramethylcyclotetrasiloxane.

Curable coating compositions according to the invention may be formed bysimply mixing components (A)-(F). The curable coating composition may beprovided in one part, although it is preferred for storage stabilityreasons, to provide the curable coating composition in two or moreparts, preferably in two parts. The two part composition may then bemixed in the required proportions prior to its use. It is important todistribute the components over the two or more parts of the curablecoating composition in the correct fashion to obtain storage stability.Accordingly, the curable coating compositions can be formulated in anumber of ways, provided that the organohydrogensiloxane and the noblemetal catalyst of component (A) are stored separately. Components (D)(i)and (D)(iii) are also preferably stored separately. Pre-reactedcombinations of components (i) and (iii) can be used. A preferred methodof storing a two part composition consists of storing as the first partof the composition, the alkenyl organopolysiloxane (A)(i), the resin(C), the noble metal catalyst, the components (D)(ii), (iii), and (iv);and in a second part, the organohydrogensiloxane of component (A), theacryloxy functional alkoxysilane or the methacryloxy functionalalkoxysilane (D)(i), and the inhibitor (B). The two parts shouldpreferably be such as to enable one to combine the reactants in a waythat permits mixing the two parts in a 10:1 to 5:1 weight ratio,preferably in a 1:1 weight ratio.

When mixed, the curable coating compositions herein should have aviscosity that is appropriate to the particular application, machineryused for applying the coating, and the substrate or synthetic textile tobe coated, but generally it is in the range 2-120 Pa·s at 25° C.Preferred materials have a viscosity in the range 8-30 Pa·s at 25° C.,and are able to cure within one-half minute at a temperature of 150-180°C. to provide elastomeric materials. Curable coating compositionsaccording to the invention should typically be capable of remaining atworkable viscosities for at least 3-6 hours when stored at temperaturesless than about 40° C.

The curable coating compositions according to the invention are usefulas coatings for a number of substrates such as fibrous materialsincluding papers and textiles, glass, and metals. The curable coatingcompositions are particularly suitable as coatings for synthetictextiles such as polyester and Nylon woven fabrics typically used in themanufacture of automotive air bags. They may also be used as protectivecoatings; as coatings to reduce permeability of the substrate such astextiles to gases including air, or for any other purpose for whichcurable coating compositions have been used. Generally, the curablecoating compositions are capable of imparting tear strength, abrasionresistance, hydrophobicity, or impact resistance, to a variety ofsubstrates. The curable coating compositions of the invention may becoated onto a substrate by any coating techniques including gravure,knife blade coating, and screen printing techniques.

Cured products can be obtained by applying the curable coatingcomposition to synthetic textiles for example by applying it to thesynthetic textile, and allowing the coated composition to cure. Curingmay be carried out by any suitable method including the application ofheat or radiation. Heating is the preferred method, and preferably attemperatures of 100-200° C., more preferably at 140-180° C. One majoradvantage is that good adhesion can be achieved after relatively shortcuring times that range from 30 seconds to an hour, generally 1-30minutes, and typically 1-15 minutes at 150° C. An increase in curingtemperature allows a shortening of the curing time.

EXAMPLES

The following examples are set forth in order to illustrate theinvention in more detail. In the Examples and Tables, the percent of thevarious components of the curable coating composition denotes thepercent by weight of the components based on the total weight of thecurable coating composition.

Comparison Example 1

A fully formulated curable coating composition was prepared by combiningComponents A-F in the amounts shown in Table 1. The composition wasapplied to a synthetic textile, and allowed to cure by the applicationof heat. The coated synthetic textile was then tested for adhesion ofthe composition to the synthetic textile by a Crease Flex Test thatdetermines the number of Crease Flex Cycles. The Crease Flex Testprotocol and the Test results are shown following the Examples.

TABLE 1 Curable Coating Composition Component Percent Description (A)(i)57.33 Organopolysiloxane with two silicon bonded alkenyl groups (A)(ii)8.77 Organohydrogensiloxane with three silicon bonded hydrogens (A)(iii)0.29 Platinum Complex (B) 0.03 1-Ethynyl-1-cyclohexanol (C) 25.97Silicone MQ Resin (D)(i) 0 Methacryloxypropyltrimethoxysilane (D)(ii)0.59 Tetraisopropoxytitanate (D)(iii) 0 Alkenyl functional silanolterminated organopolysiloxane (D)(iv) 0.29 Aluminum Acetylacetonate(D)(v) 0.31 3-Glycidoxypropyltrimethoxysilane (E) 6.18Hexamethyldisilazane treated fumed silica (F) 0.241,3,5,7-tetravinyl-1,3,5,7- tetramethylcyclotetrasiloxane

Examples 2-6

Comparison Example 1 was repeated, and five (5) fully formulated curablecoating compositions were prepared, by combining Components A-F in theamounts shown in Tables 2-6. The compositions were applied to asynthetic textile, allowed to cure, and tested for adhesion.

TABLE 2 Curable Coating Composition Component Percent Description (A)(i)57.18 Organopolysiloxane with two silicon bonded alkenyl groups (A)(ii)8.00 Organohydrogensiloxane with three silicon bonded hydrogens (A)(iii)0.29 Platinum Complex (B) 0.03 1-Ethynyl-1-cyclohexanol (C) 25.97Silicone MQ Resin (D)(i) 0.48 Methacryloxypropyltrimethoxysilane (D)(ii)0.59 Tetraisopropoxytitanate (D)(iii) 0.18 Alkenyl functional silanolterminated organopolysiloxane (D)(iv) 0.15 Aluminum Acetylacetonate(D)(v) 0.71 3-Glycidoxypropyltrimethoxysilane (E) 6.18Hexamethyldisilazane treated fumed silica (F) 0.241,3,5,7-tetravinyl-1,3,5,7- tetramethylcyclotetrasiloxane

TABLE 3 Curable Coating Composition Component Percent Description (A)(i)57.33 Organopolysiloxane with two silicon bonded alkenyl groups (A)(ii)8.33 Organohydrogensiloxane with three silicon bonded hydrogens (A)(iii)0.29 Platinum Complex (B) 0.03 1-Ethynyl-1-cyclohexanol (C) 25.97Silicone MQ Resin (D)(i) 0.48 Methacryloxypropyltrimethoxysilane (D)(ii)0.19 Tetraisopropoxytitanate (D)(iii) 0.36 Alkenyl functional silanolterminated organopolysiloxane (D)(iv) 0.29 Aluminum Acetylacetonate(D)(v) 0.31 3-Glycidoxypropyltrimethoxysilane (E) 6.18Hexamethyldisilazane treated fumed silica (F) 0.241,3,5,7-tetravinyl-1,3,5,7- tetramethylcyclotetrasiloxane

TABLE 4 Curable Coating Composition Component Percent Description (A)(i)57.18 Organopolysiloxane with two silicon bonded alkenyl groups (A)(ii)7.72 Organohydrogensiloxane with three silicon bonded hydrogens (A)(iii)0.29 Platinum Complex (B) 0.03 1-Ethynyl-1-cyclohexanol (C) 25.97Silicone MQ Resin (D)(i) 0.96 Methacryloxypropyltrimethoxysilane (D)(ii)0.39 Tetraisopropoxytitanate (D)(iii) 0.18 Alkenyl functional silanolterminated organopolysiloxane (D)(iv) 0.15 Aluminum Acetylacetonate(D)(v) 0.71 3-Glycidoxypropyltrimethoxysilane (E) 6.18Hexamethyldisilazane treated fumed silica (F) 0.241,3,5,7-tetravinyl-1,3,5,7- tetramethylcyclotetrasiloxane

TABLE 5 Curable Coating Composition Component Percent Description (A)(i)57.40 Organopolysiloxane with two silicon bonded alkenyl groups (A)(ii)8.20 Organohydrogensiloxane with three silicon bonded hydrogens (A)(iii)0.44 Platinum Complex (B) 0.005 1-Ethynyl-1-cyclohexanol (C) 26.89Silicone MQ Resin (D)(i) 0.48 Methacryloxypropyltrimethoxysilane (D)(ii)0.39 Tetraisopropoxytitanate (D)(iii) 0.18 Alkenyl functional silanolterminated organopolysiloxane (D)(iv) 0.15 Aluminum Acetylacetonate(D)(v) 0.71 3-Glycidoxypropyltrimethoxysilane (E) 4.91Hexamethyldisilazane treated fumed silica (F) 0.241,3,5,7-tetraviny1-1,3,5,7- tetramethylcyclotetrasiloxane

TABLE 6 Curable Coating Composition Component Percent Description (A)(i)59.81 Organopolysiloxane with two silicon bonded alkenyl groups (A)(ii)8.20 Organohydrogensiloxane with three silicon bonded hydrogens (A)(iii)0.44 Platinum Complex (B) 0.005 1-Ethynyl-1-cyclohexanol (C) 21.85Silicone MQ Resin (D)(i) 0.48 Methacryloxypropyltrimethoxysilane (D)(ii)0.39 Tetraisopropoxytitanate (D)(iii) 0.18 Alkenyl functional silanolterminated organopolysiloxane (D)(iv) 0.15 Aluminum Acetylacetonate(D)(v) 0.71 3-Glycidoxypropyltrimethoxysilane (E) 7.44Hexamethyldisilazane treated fumed silica (F) 0.341,3,5,7-tetravinyl-1,3,5,7- tetramethylcyclotetrasiloxaneCrease Flex Test Protocol & Results

The test protocol for measuring the Crease Flex in Cycles to Failure ofthe coated synthetic textiles prepared above, was carried out using aScott No. 363 Type Folding and Abrasion Tester sold by Test Machines,Incorporated, Ronkonkoma, N.Y., and manufactured by Toyo SeikiSeisaku-Sho, Ltd., Tokyo, Japan. This test is widely used in theindustry for measuring the fold abrasion and the resistance against foldfatigue, of synthetic textiles, rubber, and cloth. According to thestandard test protocol, two coated fabric test strips of measuring 25millimeter×120 millimeter are placed together, with the coated sidesfacing each other. The reciprocating distance of folding is set for 5centimeter. The test strips are placed in test clamps, and the appliedpressure is adjusted to 1 Kilogram. The test measures the number ofcycles of folding. The number of cycles are counted to the failure pointof lost adhesion of coating composition applied to the Nylon fabric.

The results of the Crease Flex Test are shown in Table 7. The weight ofthe coating on the 46×46 plain weave 420 denier Nylon fabric was about30 g/m².

TABLE 7 Crease Flex Test-Cycles to Failure Example Cycles to Failure1-Comparison 500 2 2,167 3 6,500 4 5,500 5 10,667 6 9,167

It can be seen in Table 7 that the curable coating compositionsaccording to the invention in Examples 2-6, that contained Components(D)(i), (D)(iii), and (D)(v), i.e., the methacryloxy functionalalkoxysilane, the alkenyl functional silanol terminatedorganopolysiloxane, and the epoxy functional alkoxysilane, producedsignificantly better results, than the curable coating composition ofComparison Example 1, that contained only the epoxy functionalalkoxysilane (D)(v).

Curable coating compositions according to this invention can be preparedby combining Components (A)-(F) in amounts within the ranges shown inTable 8.

TABLE 8 Ranges of Components (A)-(F) for Curable Coating CompositionsComponent Range (%) Description (A)(i) 45.00-70.00 Organopolysiloxanewith two silicon bonded alkenyl groups (A)(ii)  6.00-12.00Organohydrogensiloxane with three silicon bonded hydrogens (A)(iii)0.01-0.60 Platinum Complex (B) 0.005-0.075 Hydrosilylation ReactionInhibitor (C) 15.00-35.00 Silicone MQ Resin (D)(i) 0.01-5.00 Acryloxy orMethacryloxy functional alkoxysilane (D)(ii) 0.05-1.00 OrganotitaniumCompound (D)(iii) 0.01-3.00 Alkenyl functional silanol terminatedorganopolysiloxane (D)(iv) 0.01-0.30 Metal Chelate (D)(v) 0.20-2.00Epoxy functional alkoxysilane (E)  0.50-15.00 Inorganic Filler (F)0.01-0.50 Cyclic alkenyl group bearing polysiloxane

Other variations may be made in compounds, compositions, and methodsdescribed herein without departing from the essential features of theinvention. The embodiments of the invention specifically illustratedherein are exemplary only and not intended as limitations on their scopeexcept as defined in the appended claims.

1. A curable coating composition comprising: a composition curable by ahydrosilylation reaction; an acryloxy functional alkoxysilane or amethacryloxy functional alkoxysilane; an alkenyl functional silanolterminated organopolysiloxane; and an epoxy functional alkoxysilane. 2.A curable coating composition according to claim 1 wherein thecomposition curable by a hydrosilylation reaction comprises; anorganopolysiloxane having at least two silicon bonded alkenyl groups permolecule, an organohydrogensiloxane having at least three silicon bondedhydrogen atoms per molecule, and a noble metal catalyst.
 3. A curablecoating composition according to claim 1 further comprising an inhibitorfor the hydrosilylation reaction.
 4. A curable coating compositionaccording to claim 3 wherein the inhibitor is selected from the groupconsisting of acetylenic alcohols, dialkyl maleates, primary alcohols,or mixtures thereof.
 5. A curable coating composition according to claim1 further comprising a silicone resin.
 6. A curable coating compositionaccording to claim 5 wherein the silicone resin comprises an MQ resin.7. A curable coating composition according to claim 1 further comprisinga filler.
 8. A curable coating composition according to claim 7 whereinthe filler comprises microparticulate silica.
 9. A curable coatingcomposition according to claim 1 further comprising a cyclic alkenylgroup bearing polysiloxane.
 10. A curable coating composition accordingto claim 9 wherein the cyclic alkenyl group bearing polysiloxane isselected from the group consisting of1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane,1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane,pentavinylpentamethylcyclopentasiloxane, and1,3,5,7-tetra-allyl-1,3,5,7-tetramethylcyclotetrasiloxane.
 11. A curablecoating composition according to claim 9 wherein the curable coatingcomposition contains 0.01-0.05 percent by weight of the cyclic alkenylgroup bearing polysiloxane based on the total weight of the curablecoating composition.
 12. A curable coating curable coating compositionaccording to claim 1 further comprising an organotitanium compound. 13.A curable coating composition according to claim 1 further comprising ametal chelate compound.
 14. A curable coating composition according toclaim 13 wherein the metal chelate compound is selected from the groupconsisting of a triacetyl acetonate of aluminium, a tetraacetylacetonate of zirconium, and a triacetylacetonate of iron.
 15. A curablecoating composition according to claim 1 in which the acryloxyfunctional alkoxysilane is selected from the group consisting of3-acryloxypropyldimethylmethoxysilane,3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane,methacryloxymethyldimethylethoxysilane,methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane,methacryloxypropyldimethylethoxysilane,methacryloxypropyldimethylmethoxysilane,methacryloxypropylmethyldiethoxysilane,methacryloxypropylmethyldimethoxysilane,methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane,methacryloxypropyltrisisopropoxysilane, andmethacryloxypropyltrismethoxyethoxysilane.
 16. A curable coatingcomposition according to claim 1 wherein the curable coating compositioncontains 0.01-2.00 percent by weight of the acryloxy functionalalkoxysilane or methacryloxy functional alkoxysilane based on the totalweight of the curable coating composition.
 17. A curable coatingcomposition according to claim 1 in which the alkenyl functional silanolterminated organopolysiloxane has the formula H—(OSiR²₂)_(m)(OSiR²R′)_(n)—OH wherein R² is an alkyl group having 1-8 carbonatoms or an aryl group having 6-8 carbon atoms; R′ is a monovalentunsaturated hydrocarbon group having 2-8 carbon atoms; and m and n areeach 1-6.
 18. A curable coating composition according to claim 1 whereinthe curable coating composition contains 0.01-3.00 percent by weight ofthe alkenyl functional silanol terminated organopolysiloxane based onthe total weight of the curable coating composition.
 19. A curablecoating composition according to claim 1 in which the epoxy functionalalkoxysilane is selected from the group consisting of2-(3,4-epoxycyclohexyl)ethyltriethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,5,6-epoxyhexyltriethoxysilane, 3-glycidoxypropyldimethylethoxysilane,3-glycidoxypropylmethyldiethoxysilane,3-glycidoxypropylmethyldimethoxysilane,3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyltrimethoxysilane.20. A curable coating composition according to claim 1 wherein thecurable coating composition contains 0.20-2.00 percent by weight of theepoxy functional alkoxysilane based on the total weight of the curablecoating composition.
 21. A textile coated with a cured coatingcomposition according to claim
 1. 22. A textile according to claim 21further defined as an automotive air bag.
 23. A method of coating atextile with the curable coating composition according to claim 1, saidmethod comprising the step of applying the curable coating compositionto the textile.
 24. A method according to claim 23 further comprisingthe step of applying heat to the curable coating composition afterapplication to the textile for promoting cure of the curable coatingcomposition.
 25. A method according to claim 24 wherein heat is appliedat a temperature of from 100-200° C.
 26. A method according to claim 25wherein heat is applied for a period of time of from 30 seconds to anhour.
 27. A method according to claim 23 further comprising the stepapplying radiation to the curable coating composition after applicationto the textile for promoting cure of the curable coating composition.28. A method according to claim 23 wherein the textile is furtherdefined as an automotive air bag.
 29. A two-part curable coatingcomposition comprising: I) a first-part of the composition comprising;an organopolysiloxane having at least two silicon bonded alkenyl groupsper molecule, a silicone resin, an organotitanium compound, an alkenylfunctional silanol terminated organopolysiloxane, a metal chelatecompound, and an epoxy functional alkoxysilane, and optionally, a noblemetal catalyst; and II) a second-part of the composition comprising; anorganohydrogensiloxane having at least three silicon bonded hydrogenatoms per molecule, an inhibitor, and an acryloxy functionalalkoxysilane or a methacryloxy functional alkoxysilane.
 30. A two-partcurable coating composition according to claim 29 comprising said noblemetal catalyst.
 31. A two-part curable coating composition according toclaim 29 further comprising a filler.
 32. A two-part curable coatingcomposition according to claim 29 further comprising a cyclic alkenylgroup bearing polysiloxane.